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摘要: 长白山地区位于滨太平洋新生代火山区，区内粗面玄武岩广泛分布，面积近20000 km2。该区粗面玄武岩中稀土元素含量很高，如何开采利用不仅取决于其含量，还取决于其赋存状态，但这方面的研究迄今未见报道。本文采用电感耦合等离子体光谱法分析长白山地区火山岩中的主量元素，获得其岩相组成信息，采用电感耦合等离子体质谱法分析稀土元素，由此得到其地球化学特征，并结合分级提取实验，初步探讨长白山火山岩中稀土元素赋存状态。元素分析结果表明，研究区内火山岩的岩性主要以粗面玄武岩和粗面岩为主，稀土元素的总量(∑REEs)为211～893 μg/g，其中以粗面岩显著富集稀土元素;粗面岩的δEu为0.06～0.69，具有强烈的负铕异常特性，轻稀土元素与重稀土元素总量比值(∑LREEs/∑HREEs)为3.80～5.61，反映了该区轻、重稀土元素分馏程度较高，且具有富集轻稀土元素的特性。稀土元素的主要赋存状态为磷酸盐结合态(52.9%～88.5%)、碳酸盐结合态(14.6%～43.8%)、氧化物结合态(6.04%～18.4%)，而以硅酸盐结合态和离子吸附态存在的稀土元素所占比例最少。分级提取实验分析结果表明，样品的稀土元素总量提取率为91.1%～108%，表明此分级提取方法适合于火山岩中稀土元素赋存状态的分析，为类似火山岩中稀土元素的赋存状态研究提供一种可行性参考方法。Abstract: Changbai Mountain is located in the circum-pacific Cenozoic volcanic region, where basalt is widely distributed over nearly 20000 km2, and in which, high contents of rare earth elements (REEs) have been reported. As it is known, the value for utilization of such REE resources depends not only on their contents but also on their existing characteristics, however, no related reports have been made in this respect about the REEs in the Changbai Mountain area so far. In this work, using Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), the main component elements and rare earth elements in the volcanic rocks from Changbai Mountain were both accurately determined, the results revealing that the composition of the rocks is similar to lithofacies of basalt and trachyte, and the amount of the REEs was as high as 211-893 μg/g, with REEs enrichment being more easily found in the latter. Furthermore, negative europium anomalies (δEu) of 0.06-0.69 were observed, and the ratios of light rare earth elements and heavy rare earth elements (∑LREEs/∑HREEs) had a range of 3.80-5.61, which meant that the LREEs were prone to be more enriched. Finally, a grade extraction procedure was carried out to study the REEs existing phases, the results show that the REEs mainly exist as phosphate phase (52.9%-88.5%), carbonate phase (14.6%-43.8%) and oxides (6.04%-18.4%), while those of silicate phase and ion adsorption phase were the least. The grade extraction procedure was proven to be accurate, with recovery yields of 91.1%-108%, providing a feasible strategy for similar analytical purposes.
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Key words:
- Changbai Mountain volcanic rocks /
- trachybasalt /
- trachyte /
- rare earth elements /
- existing phases
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表 1 分级提取流程
Table 1. Grading sequential extraction procedure
形态 提取试剂 操作条件 离子吸附态 30 g/L硫酸铵溶液(pH=5) 室温超声1 h，隔夜放置 碳酸盐结合态 3%过氧化氢-12.5%盐酸 沸水浴中加热1 h 氧化物结合态 高氯酸 微沸30 min，加水稀释 磷酸盐结合态 过氧化钠，盐酸 700℃烧结30 min，冷却后以盐酸提取 硅酸盐结合态 硝酸，氢氟酸，高氯酸 参照2.2.2 节 
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表 2 ICP-AES分析长白山火山岩的主量元素含量
Table 2. The content of main elements in Changbai Mountain volcanic rocks by ICP-AES
样品编号 w/% SiO2 Al2O3 Fe2O3 Na2O K2O CaO MgO TiO2 MnO2 C-1 50.1 16.3 13.5 3.01 2.88 5.72 3.3 2.73 0.27 C-2 49.5 16.1 13.4 3.11 2.91 60.1 3.41 2.82 0.22 C-3 51.5 15.7 12.5 3.49 2.94 5.69 3.07 2.53 0.21 C-4 48.9 16.1 13.8 4.21 2.61 6.17 3.52 2.27 0.22 C-5 52.4 17.4 12.7 3.69 3.06 0.76 4.84 3.98 0.21 C-6 60.1 17.5 6.78 4.87 4.83 2.44 0.81 0.67 0.17 C-7 59.3 17.7 7.22 4.89 4.72 2.48 0.84 0.69 0.24 C-8 61.4 17.6 5.59 4.96 6.08 2.26 0.71 0.57 0.13 C-9 66.4 14.3 6.41 4.98 5.52 0.71 0.05 0.04 0.13 C-10 67.5 14.2 6.01 4.97 5.22 0.25 0.02 0.02 0.23 C-11 70.2 12.6 5.71 4.65 5.24 0.57 0.05 0.04 0.17 C-12 70.3 12.6 5.67 4.75 5.13 0.61 0.04 0.03 0.14 C-13 68.4 12.4 5.73 4.92 5.11 0.62 0.04 0.03 0.16 C-14 69.6 12.4 5.58 4.49 5.12 0.61 0.04 0.03 0.15 C-15 65.9 14.9 4.91 4.87 5.97 1.41 0.23 0.19 0.17 C-16 69.7 13.0 5.82 3.66 5.97 0.48 0.04 0.03 0.14 C-17 63.8 16.9 5.19 4.78 6.49 1.49 0.21 0.17 0.16
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表 3 长白山火山岩样品的各稀土元素含量
Table 3. Content of REE in Changbai Mountain volcanic rocks
样品编号 w/(μg·g-1) ΣREEs ΣLREEs ΣHREEs 
δEu δCe La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Y C-1 43.3 117 9.68 41.1 8.04 2.76 8.24 1.24 5.71 1.04 2.88 0.39 2.61 0.39 26.3 271 222 48.8 4.55 1.16 1.19 C-2 47.1 97.1 10.8 46.5 8.68 3.12 9.46 1.19 6.47 1.18 3.09 0.39 2.61 0.35 31.3 269 213 56.1 3.80 1.17 0.90 C-3 49.3 100 11.6 48.7 10.1 3.27 9.47 1.27 7.14 1.14 2.93 0.43 2.96 0.45 32.2 281 223 58.0 3.84 1.14 0.87 C-4 43.5 89.6 9.81 44.2 8.76 2.79 8.93 1.21 6.09 1.01 2.92 0.35 2.48 0.33 28.8 251 199 52.1 3.81 1.08 0.90 C-5 37.2 75.6 8.5 35.8 7.36 2.78 7.34 0.97 4.93 0.91 2.46 0.27 1.89 0.27 24.4 211 167 43.4 3.85 1.29 0.89 C-6 70.2 195 15.4 60.6 10.5 3.46 10.3 1.34 7.33 1.19 3.48 0.43 3.51 0.55 35.2 419 355 63.3 5.61 1.13 1.24 C-7 69.8 142 15.6 60.2 10.1 3.62 9.98 1.31 7.01 1.21 3.21 0.48 3.34 0.56 33.7 362 301 60.8 4.96 1.23 1.22 C-8 66.1 204 14.2 55.8 11.3 2.25 10.9 1.52 7.51 1.41 3.84 0.57 3.59 0.41 36.9 420 354 66.7 5.30 0.69 1.39 C-9 162 297 31.9 120 22.9 0.36 21.6 3.35 18.4 3.39 9.22 1.31 7.91 1.06 87.8 788 634 154 4.12 0.06 0.86 C-10 165 266 34.2 130 23.4 0.39 20.9 3.13 17.3 3.02 8.74 1.16 7.85 1.11 80.1 762 619 143 4.32 0.06 0.74 C-11 175 330 35.9 130 25.1 0.52 24.1 3.61 20.4 3.74 10.8 1.41 9.26 1.25 97.2 868 697 172 4.06 0.07 0.87 C-12 166 380 33.1 120 22.7 0.51 22.9 3.38 18.5 3.42 10.4 1.41 8.56 1.18 88.2 880 722 158 4.57 0.08 1.07 C-13 175 332 35.1 132 24.9 0.45 23.7 3.53 19.8 3.68 10.3 1.33 9.18 1.36 95.7 868 700 169 4.15 0.06 0.88 C-14 159 355 32.9 121 23.1 0.46 22.3 3.31 18.9 3.51 9.92 1.29 8.26 1.22 85.3 845 691 154 4.49 0.07 1.02 C-15 66.4 180 13.7 54.1 9.69 0.92 8.73 1.31 7.56 1.41 3.34 0.48 3.16 0.47 32.8 384 325 59.3 5.48 0.34 1.25 C-16 182 342 36.5 132 26.4 0.54 24.3 3.74 20.3 3.86 11.1 1.53 9.18 1.39 97.9 893 719 173 4.15 0.07 0.87 C-17 66.0 179 14.2 52.9 9.72 0.87 9.58 1.38 6.81 1.21 3.38 0.46 2.96 0.54 32.1 381 323 58.4 5.52 0.31 1.22
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表 4 火山岩样品中稀土元素在各赋存相态中的含量
Table 4. REE contents of different existing phases in Changbai Mountain volcanic rocks
样品编号 w/(μg·g-1) 硅酸盐相 离子吸附相 氧化物相 碳酸盐相 磷酸盐相 C-1 5.66 5.93 30.3 40.1 192 C-2 8.36 5.02 33.9 66.1 180 C-3 9.91 5.75 54.6 50.8 176 C-4 3.65 7.76 29.6 54.6 184 C-5 1.61 35.6 40.0 37.8 129 C-6 17.3 20.8 38.3 220 143 C-7 18.3 21.7 47.2 226 122 C-8 15.6 21.8 16.3 162 215 C-9 15.7 149 86.5 406 270 C-10 3.40 115 53.9 510 210 C-11 5.22 30.8 30.6 64.8 802 C-12 6.98 219 131 84.7 653 C-13 8.82 37.4 45.0 68.0 837 C-14 7.78 113 65.2 156 592 C-15 2.96 14.9 7.46 20.9 357 C-16 3.93 14.5 21.4 87.1 771 C-17 3.31 4.45 10.5 23.8 309
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表 5 长白山火山岩中分级提取实验总稀土提取率
Table 5. The extraction efficiency of total REEs from the Changbai Mountain volcanic rocks by the grading sequential extraction procedure
样品编号 w/(μg·g-1) 提取率/% 分级提取的稀土总量 稀土总量 C-1 268 271 98.9 C-2 288 269 107 C-3 291 281 104 C-4 272 251 108 C-5 208 211 98.8 C-6 419 419 100 C-7 418 413 101 C-8 409 420 97.4 C-9 778 788 98.8 C-10 777 762 102 C-11 903 868 104 C-12 876 880 100 C-13 936 958 97.7 C-14 821 845 97.2 C-15 388 384 101 C-16 883 893 98.9 C-17 347 381 91.1
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[1] 倪平鹏,蒙运兵,杨斌.我国稀土资源开采利用现状及保护性开发战略[J].宏观经济研究,2010(10): 13-20. http://www.cnki.com.cn/Article/CJFDTOTAL-JJGA201010004.htm
[2] 程建忠,车丽萍.中国稀土资源开采现状及发展趋势[J].稀土,2010,31(2):65-69. http://www.cnki.com.cn/Article/CJFDTOTAL-XTZZ201002020.htm
[3] 陈吉艳,杨瑞东,张杰.贵州织金含稀土磷矿床稀土元素赋存状态研究[J].矿物学报,2010,30(1):123-129. http://www.cnki.com.cn/Article/CJFDTOTAL-KWXB201001017.htm
[4] 罗明标,杨枝,郭国林,李伯平,刘峰,刘维.白云鄂博铁矿石中稀土的赋存状态研究[J].中国稀土学报,2007,25(1):57-61. http://www.cnki.com.cn/Article/CJFDTOTAL-XTXB2007S1015.htm
[5] 周殉若,宋新华,郑济林.某些花岗岩中稀土元素赋存状态的研究[J].武汉地质学院学报,1987,12(3):277-284. http://www.cnki.com.cn/Article/CJFDTOTAL-DQKX198703009.htm
[6] 杨武斌,牛贺才,单强,罗勇,于学元,裘愉卓.巴尔哲超大型稀有稀土矿床成矿机制研究[J].岩石学报,2009,25(11):2924-2932. http://www.cnki.com.cn/Article/CJFDTOTAL-YSXB200911023.htm
[7] Zhao Z H, Xiong X L, Han X D, Wang Y X, Wang Q, Bao Z W, Jahn B M.Control on the REE tetrad effect in granites:Evidence from the Qianlishan and Baerzhe granites [J].Geochemical Journal,2002,36(6):527-543. doi: 10.2343/geochemj.36.527
[8] 柏静儒,王擎,魏艳珍,柳桐.桦甸油页岩中稀土元素赋存状态研究[J].燃料化学学报,2011,39(7):489-493. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX201107001.htm
[9] 杨瑞东,王伟,鲍淼,王强,魏怀瑞.贵州赫章二叠系粗面玄武岩顶部稀土矿床地球化学特征[J].矿床地质,2006,25(Z1):205-208.
[10] 王伟,杨瑞东,栾进华,黄波.贵州西部粗面玄武岩风化壳中稀土矿成矿机理及成矿模式[J].四川地质学报,2011,31(4):420-423. http://www.cnki.com.cn/Article/CJFDTOTAL-SCDB201104012.htm
[11] 刘若新,李继泰,魏海泉,许东满,郑祥身.长白山天池火山——一座具潜在喷发危险的近代火山[J].地球物理学报,1992,35(5):661-665. http://www.cnki.com.cn/Article/CJFDTOTAL-DQWX199205018.htm
[12] Liu R X,Fan Q C,Zheng X S,Zhang M,Li N.The magma evolution of Tianchi volcano Chang baishan [J].Science in China: Series D(Earth Sciences),1998,41(4):382-389. doi: 10.1007/BF02932689
[13] 樊祺诚,隋建立,孙谦,李霓,王团华.天池火山千年大喷发的岩浆混合作用与喷发机制初步探讨[J].岩石学报,2005,21(6):1703-1708. http://www.cnki.com.cn/Article/CJFDTOTAL-YSXB200506019.htm
[14] 隋建立,樊祺诚,刘嘉麒,郭正府.长白山火山地幔不均一性——微量元素及同位素地球化学研究[J].岩石学报,2007,23(6):1512-1520. http://www.cnki.com.cn/Article/CJFDTOTAL-YSXB200706024.htm
[15] 樊祺诚,隋建立,王团华,李霓,孙谦.长白山天池火山粗面玄武岩的喷发历史与演化[J].岩石学报,2006,22(6):1449-1457. http://www.cnki.com.cn/Article/CJFDTOTAL-YSXB200606001.htm
[16] Fan Q C, Sun Q, Li N, Wang T H.Holocene volcanic rocks in Jingbo Lake region: Diversity of magmatism[J].Progress in Natural Science,2006,16(1):65-71. doi: 10.1080/10020070612331343193
[17] Guo Z F, Liu J Q, Han J T, He H Y, Dau G L, You H T.Effect of gas emissions from Tianchi volcano (NE China) on environment and its potential volcanic hazards[J].Science in China: Series D (Earth Sciences),2006,49(3):304-310. doi: 10.1007/s11430-006-0304-x
[18] 邹海波,樊祺诚.中国年轻火山岩铀钍(U-Th)非平衡研究进展[J].岩石学报,2011,27(10):2821-2826. http://www.cnki.com.cn/Article/CJFDTOTAL-YSXB201110002.htm
[19] 冯晅,迟唤昭,刘财,田有,柳云龙,郑确.长白山及邻区地壳、上地幔顶部三维速度结构[J].吉林大学学报(地球科学版),2013,43(3):983-992. http://www.cnki.com.cn/Article/CJFDTOTAL-CCDZ201303038.htm
[20] 田丰,汤德平.吉林省长白山地区新生代火山岩的特点及其成因[J].岩石学报,1989,5(2):49-64. http://www.cnki.com.cn/Article/CJFDTOTAL-YSXB198902006.htm
[21] 金伯禄,张希友.长白山火山地质研究[M].延吉:东北朝鲜民族教育出版社,1994:206-207.
[22] 刘嘉麒.中国火山[M].北京:科学出版社,1999:1-219.
[23] 赵海玲,邓晋福,陈发景,胡泉,赵世柯.东北地区新生代火山作用、深部作用与大陆裂谷型盆地[J].地球科学——中国地质大学学报,1996,21(6):615-619. http://www.cnki.com.cn/Article/CJFDTOTAL-DQKX606.016.htm
[24] 孙春强.长白山天池火山岩石学与岩浆演化特征研究[D].北京:中国地震局地质研究所,2008:63-65.
[25] 李霓,樊棋诚,孙谦,张文兰.长白山天池火山岩浆演化——来自主矿物成分的证据[J].岩石学报,2004,20(3):575-582. http://www.cnki.com.cn/Article/CJFDTOTAL-YSXB200403021.htm
[26] 樊棋诚.长白山火山的历史与演化[J].资源调查与环境,2008,29(3):196-203. http://www.cnki.com.cn/Article/CJFDTOTAL-HSDZ200803005.htm
[27] 龚美菱.相态分析与地质找矿[M].北京:地质出版社,2007:77-80.
[28] Le Bas M J, Le Maitre R W, Streckeisen A, Zanttin B.A chemical classification of volcanic rocks based on the total alkalisilica diagram [J].Journal of Petrology,1986,27(3):745-750. doi: 10.1093/petrology/27.3.745
[29] Le Maitre R W, Bateman P, Dudet A, Keller J, Le Bas M J, Sabine P A, Schmid R, Sorensen H, Streckeisen A, Woodley A R, Zanettiu B.A classification of igneous rocks and a glassary of terms[M].Oxford: Blackwell Press,1989:192-194.
[30] 陈德潜,陈刚.实用稀土元素地球化学[M].北京:冶金工业出版社,1990:57-231.
[31] 樊祺诚,刘若新,魏海泉,隋建立,李霓.长白山天池全新世喷发与岩石地球化学特征[J].地质论评,1999,45(Z1):263-271. doi: 10.3321/j.issn:0371-5736.1999.z1.036
[32] Basu A R, Wang J W, Huang W K, Xie G H, Tatsumoto M.Major element, REE, and Pb, Nd and Sr geochemistry of Cenozoic Volcanic rocks of eastern China:Implications for their origin from suboceanic type mantle reservoirs[J].Earth and Planetary Science Letters, 1991,105(1-3):149-169. doi: 10.1016/0012-821X(91)90127-4
[33] 李建康,陈振宇,陈郑辉,侯可军,赵正.江西赣县韩坊岩体的成岩时代及成矿条件分析[J].岩矿测试,2012,31(4):717-723. http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201204030.htm
[34] 杨瑞东,王伟,鲍淼,王强,魏怀瑞.贵州赫章二叠系粗面玄武岩顶部稀土矿床地球化学特征[J].矿床地质,2006,25(Z1):205-208.
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